Use of pentamethylindanol derivatives in augmenting or enhancing the aroma or taste of smoking tobacco compositions or smoking tobacco articles

ABSTRACT

Described are tertiary pentamethylindanol derivatives defined according to the structure: ##STR1## wherein the dashed line represents a carbon-carbon single or a carbon-carbon double bond and uses thereof in augmenting or enhancing the aroma or taste of smoking tobaccos or smoking tobacco compositions.

This is a division of application Ser. No. 589,662 filed Mar. 14, 1984now U.S. Pat. No. 4,520,032.

BACKGROUND OF THE INVENTION

The present invention relates to tertiary pentamethylindanol derivativesdefined according to the structure: ##STR2## wherein the dashed linerepresents a carbon-carbon single bond or a carbon-carbon double bondand uses of such compounds in augmenting or enhancing the aroma or tasteof perfume compositions, perfumed articles, colognes, foodstuffs,smoking tobacco compositions and smoking tobacco articles.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) flavors andfragrances to (or in) various consumable materials. Such substances areused to diminish the use of expensive natural materials some of whichmay be in short supply and to provide more uniform properties in thefinished product.

Leafy, patchouli-like, vetiver-like, ginseng-like, piney, rooty, woodyand camphoraceous aromas with leafy, green, camphoraceous, woody,patchouli-like, musk, rooty, earthy and piney undertones areparticularly desirable in several types of perfume compositions,perfumed articles and colognes.

Musky, patchouli-like and earthy aromas and musky tastes are useful inseveral types of foodstuffs, particularly walnut flavored foodstuffs andblackberry flavored foodstuffs.

Woody and oriental aroma and taste nuances are highly desirable inaugmenting or enhancing the aromas and tastes of smoking tobacco bothprior to and on smoking in the main stream and the side stream.

Pentamethylindanols are known to be useful in the fields of perfumery.Thus, U.S. Pat. No. 3,636,165 discloses the compound defined accordingto the structure: ##STR3## as being useful in augmenting or enhancingthe aroma of perfume compositions and perfumed articles. This compoundis disclosed in U.S. Pat. No. 3,636,165 to be produced from epoxypentamethylindane according to the reaction: ##STR4## whereby thecompound having the structure: ##STR5## is reacted with aluminumisopropoxide and the workup is carried out under acidic conditions.

Nothing in the prior art however, discloses the preparation of tertiarypentamethylindanol derivatives which have unexpected, unobvious andadvantageous organoleptic characteristics when compared to the chemicalsof the prior art.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the crude reaction product of Example Icontaining the compound defined according to the structure: ##STR6##

FIG. 2 is the GLC profile for Fraction 2 of the first distillation ofthe reaction product of Example I containing the compound having thestructure: ##STR7##

FIG. 3 is the GLC profile for Fraction 7 of the second distillation ofthe reaction product of Example I containing the compound having thestructure: ##STR8##

FIG. 4 is the GC-MS profile for the compound having the structure:##STR9## produced according to Example I.

FIG. 5 is the NMR spectrum for Fraction 7 of the distillation of thereaction product of Example I containing the compound having thestructure: ##STR10## (conditions: Field strength: 100 MHz; Solvent:CFCl₃).

FIG. 6 is the Infra-red spectrum for the compound having the structure:##STR11## produced according to Example I.

FIG. 7 is the GLC profile for Fraction 5 of the distillation of thereaction product of Example II containing the compound having thestructure: ##STR12##

FIG. 8 is the NMR spectrum for Fraction 5 of the distillation of thereaction product of Example II containing the compound having thestructure: ##STR13## (conditions: Field strength: 100 MHz; Solvent:CFCl₃).

FIG. 9 is the GLC profile for Fraction 3 of the distillation of thereaction product of Example III containing the compound having thestructure: ##STR14##

FIG. 10 is the GLC profile for Fraction 4 of the first distillation ofthe reaction product of Exmple IV containing the compound having thestructure: ##STR15##

FIG. 11 is the GLC profile for Fraction 4 of the second distillation ofthe reaction product of Example IV containing the compound having thestructure: ##STR16##

FIG. 12 is the NMR spectrum for Fraction 4 of the distillation of thereaction product of Example IV containing the compound having thestructure: ##STR17##

FIG. 13 represents a cut-away side elevation view of apparatus used informing perfumed polymers which contain imbedded therein at least one ofthe tertiary pentamethylindanol derivatives of our invention.

FIG. 14 is a front view of the apparatus of FIG. 13 looking in thedirection of the arrows.

DETAILED DESCRIPTION OF THE DRAWINGS

Referring to FIGS. 13 and 14, there is provided a process for formingscented polymer elements (wherein the polymer may be a thermoplasticpolymer such as low density polyethylene or polypropylene or copolymersof ethylene and vinyl acetate or mixtures of polymers and copolymerssuch as copolymers of ethylene and vinyl acetate and polyethylene) suchas pellets useful in the formation of plastic particles useful infabricating certain articles which may be perfumed. This processcomprises heating the polymer or mixture of polymers to the meltingpoint of said polymer or mixture of polymers, e.g., 250° C. in the caseof low density polyethylene. The lower most portion of the container ismaintained at a slightly low temperature and the material in thecontainer is taken off at such location for delivery through theconduit. Thus, referring to FIGS. 13 and 14, in particular, theapparatus used in producing such elements comprises a device for formingthe polymer containing perfume e.g., polyethylene orpolyethylene-polyvinyl acetate or mixtures of same or polypropylene,which comprises a vat or container 212 into which the polymer takenalone or in admixture with other copolymers and the perfuming substancewhich is at least one of the tertiary pentamethylindanol derivatives ofour invention or mixtures of the tertiary pentamethylindanol derivativesand other compatible perfumes is placed. The container is closed bymeans of an air-tight lid 228 and clamped to the container by bolts 265.A stirrer 273 traverses the lid or cover 228 in an air-tight manner andis rotatable in a suitable manner. A surrounding cylinder 212A havingheating coils which are supplied with electric current through cable 214from a rheostat or control 216 is operated to maintain the temperatureinside the container 212 such that the polymer in the container will bemaintained in the molten or liquid state. It has been found advantageousto employ polymers at such a temperature that the viscosity will be inthe range of 90-100 sayboldt seconds. The heater 218 is operated tomaintain the upper portion of the container 212 within a temperaturerange of, for example, 220°-270° C. in the case of low densitypolyethylene. The bottom portion of the container 212 is heated by meansof heating coils 212A regulated through the control 220 connectedthereto through a connecting wire 222 to maintain the lower portion ofthe container 212 within a temperature range of 220°-270° C.

Thus, the polymer or mixture of polymers added to the container 212 isheated from 10-12 hours, whereafter the perfume composition or perfumematerial which contains one or more of the tertiary pentamethylindanolderivatives of our invention is quickly added to the melt. Generally,about 10-45 percent by weight of the resulting mixture of the perfumerysubstance is added to the polymer.

After the perfume material is added to the container 212, the mixture isstirred for a few minutes, for example, 5-15 minutes and maintainedwithin the temperature ranges indicated previously by the heating coil212A. The controls 216 and 220 are connected through cables 224 and 226to a suitable supply of electric current for supplying the power forheating purposes.

Thereafter, the valve "V" is opened permitting the mass to flowoutwardly through conduit 232 having a multiplicity of orifices 234adjacent to the lower side thereof. The outer end of the conduit 232 isclosed so that the liquid polymer in intimate admixture with one or moreof the tertiary pentamethylindanol derivatives of our invention ormixture of tertiary pentamethylindanol derivatives and one or more othersubstances, will continuously drop through the orifices 234 downwardlyfrom the conduit 232. During this time, the temperature of the polymerintimately admixed with the perfumery substance in the container 212 isaccurately controlled so that a temperature in the range of from about240°-250° C., for example, (in the case of low density polyethylene)will exist in the conduit 232. The regulation of the temperature throughthe controls 216 and 220 is essential in order to insure temperaturebalance to provide for the continuous dripping or dropping of moltenpolymer intimately admixed with the perfume substance which is all of orwhich contains one or more of the tertiary pentamethylindanolderivatives of our invention, through the orifices 234 at a rate whichwill insure the formation of droplets 236 which will fall downwardlyonto a moving conveyor belt 238 caused to run between conveyor wheels240 and 242 beneath the conduit 232.

When the droplets 236 fall onto the conveyor 238, they form pellets 244which harden almost instantaneously and fall off the end of the conveyor238 into a container 250 which is advantageously filled with water orsome other suitable cooling liquid to insure the rapid cooling of eachof the pellets 244. The pellets 244 are then collected from thecontainer 250 and utilized for the formation of other functionalproducts, e.g., garbage bags and the like.

THE INVENTION

The present invention provides tertiary pentamethylindanol derivativesdefined according to the generic structure: ##STR18## wherein the dashedline represents a carbon-carbon single bond or a carbon-carbon doublebond.

The tertiary pentamethylindanol derivatives of our invention producedaccording to the processes of our invention are capable of augmenting orenhancing musky, patchouli-like and earthy aromas with musky tastecharacteristics of foodstuffs, foodstuff flavors, chewing gums, chewinggum flavors, medicinal products, medicinal product flavors, toothpastesand toothpaste flavors.

The tertiary pentamethylindanol derivatives of our invention as well asmixtures thereof are also capable of modifying or enhancing the aromacharacteristics of perfume compositions, colognes and perfumed articles(including soaps, nonionic, anionic, cationic and zwitterionicdetergents, fabric softener articles and perfumed polymers) by impartingthereto, leafy, patchouli-like, vetiver-like, ginseng-like, piney,rooty, woody and camphoraceous aromas with leafy, green, camphoraceous,woody, patchouli-like, musk, rooty, earthyl and piney undertones, thusfulfilling a need the field of perfumery.

In tobacco, tobacco flavoring, substitute tobacco and substitute tobaccoflavoring compositions, the tertiary pentamethylindanol derivatives ofour invention produced according to the process of our invention augmentor enhance or impart woody, oriental-like and Turkish tobacco-like aromaand taste nuances to smoking tobacco and substitute smoking tobaccosprior to and on smoking in both the main stream and the side stream.

The tertiary pentamethylindanol derivatives of our invention areproduced using as a starting material the epoxide derivative definedaccording to the structure: ##STR19## which, in turn, is producedaccording to the procedure of U.S. Pat. No. 3,647,826 issued on Mar. 7,1972 the disclosure of which in incorporated by reference herein. Thegeneric reaction to produce the compound defined according to thestructure: ##STR20## is shown thusly: ##STR21## When producing thecompound defined according to the structure: ##STR22## an aluminumalkoxide catalyst defined according to the structure: ##STR23## whereinR represents C₃ or C₄ alkyl is used followed by a workup using base (asopposed to acid, at a pH of less than 7). This reaction is shown thusly:##STR24## When using an acidic workup, the secondary alcohol definedaccording to the structure: ##STR25## is formed rather than the tertiaryalcohol having the structure: ##STR26## and, thus, the secondary alcoholhaving the structure: ##STR27## is formed according to the reaction:##STR28## as per the teachings of U.S. Pat. No. 3,636,165 issued on Jan.18, 1972, the specification for which is incorporated by referenceherein.

In carrying out the reaction: ##STR29## wherein R represents C₃ -C₄alkyl, the reaction is carried out at reflux conditions at a temperaturein the range of from about 90° C. up to about 130° C. in the presence ofan inert non-reactive solvent, that is, non-reactive to the epoxideproduct having the structure: ##STR30## or the tertiarypentamethylindanol derivative having the structure: ##STR31## Typicalsolvents are toluene and xylene. The reaction pressure may vary from 0.8atmospheres up to about 2 atmospheres with a pressure of 1 atmospherebeing most convenient. The reaction time may vary from about one hour upto about thirty hours, greater reaction times giving rise to greateryields.

At the end of the reaction, the reaction mass is admixed with water andaqueous base at a pH of between about 9 and 11. The resulting reactionmass is then washed with water and the organic phase is then distilled,preferably by means of fractional distillation. Fractions of theresulting distillate are then selected for their organolepticproperties.

The tertiary pentamethylindanol derivative defined according to thestructure: ##STR32## may be prepared from the epoxide having thestructure: ##STR33## by means of reaction with lithium aluminum hydrideor reaction with a mixture of lithium and ethylene diamine according toone of the reactions: ##STR34##

The reaction with lithium aluminum hydride and the compound having thestructure: ##STR35## is carried out under reflux conditions at atemperature in the range of from about 160° C. up to about 200° C. atatmospheric pressure. The time of reaction may vary from about two hoursup to about thirty hours with the optimum reaction time being in therange of from about nine hours up to about twelve hours when carryingout the reaction at reflux at a temperature of between 170° C. and 180°C. The reaction is carried out in the presence of a solvent suitable tomaintain the above-mentioned reaction conditions, e.g., diglime whichwill cause the reaction to be carried out at about 170°-180° C. at oneatmosphere pressure. The mole ratio of lithium aluminum hydride: toepoxide having the structure: is about 1:1. At the end of the reaction,the reaction mass is quenched with water and base such as aqueous dilutesodium hydroxide. The organic layer is then separated and distilled andthe resulting fractions are bulked and utilized for their organolepticproperties.

When carrying the reaction of the compound having the structure:##STR36## with lithium and ethylene diamine, according to the reaction:##STR37## the reaction is carried out at a temperature of between 45°and 60° C. at atmospheric pressure for a period of time of between aboutone and about three hours. An excess of ethylene diamine is used and,accordingly, the mole ratio of ethylene diamine:epoxide definedaccording to the structure: ##STR38## may vary from about 2:1 up toabout 5:1. The mole ratio of lithium metal:ethylene diamine may varyfrom about 0.9:1 up to about 1:0.9 with the ethylene diamine beingpreferred to be in molar excess. At the end of the reaction, thereaction mass is quenched with water and extracted with a solvent suchas diethyl ether. The extract is stripped of solvent and distilledpreferably by means of fractional distillation. The resulting fractionsare bulked and utilized for their organoleptic properties.

The following table sets forth the reaction products of our inventionand their corresponding organoleptic properties:

                  TABLE I                                                         ______________________________________                                        Structure of                                                                  Reaction Perfume     Food Flavor Tobacco Flavor                               Product  Properties  Properties  Properties                                   ______________________________________                                         ##STR39##                                                                             A leafy, patchouli-like, vetiver-like, and ginseng- like aroma                with leafy, green, camphoraceous, woody, patchouli-like and musk              ndertones.  A musky, patchouli-like and earthy aroma with a                               musky taste at 1.0 ppm causing it to be useful in                             walnut and blackberry flavors.                                                            A woody, oriental aroma and taste both                                        prior to and on smoking in the main                                           stream and the side stream.                   ##STR40##                                                                             A patchouli- like, piney, rooty, woody, camphoraceous  aroma                  with rooty, earthy, camphoraceous, woody and piney under-                                 A patchouli- like aroma and taste profile at 5.0 ppm                          ausing it to be useful in walnut flavors.                                                 An oriental, Turkish tobacco aroma and                                        taste profile both prior to and on                                            smoking in the main stream and the side                                       stream.                                      ______________________________________                                    

When the tertiary pentamethylindanol derivatives produced according tothe process of our invention are used as food flavor adjuvants, thenature of the co-ingredients included with the tertiarypentamethylindanol derivatives used in formulating the productcomposition will also serve to alter, modify, augment or enhance theorganoleptic characteristics of the ultimate foodstuff treatedtherewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms means "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, chewing gums, vegetables, cereals, soft drinks,snacks and the like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay rubber orcertain comesible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine; and a flavoring composition whichincorporates the tertiary pentamethylindanol derivatives of ourinvention and, in addition, sweetening agents which may be sugars,including sucrose or dextrose and/or artificial sweeteners such ascyclamates or saccharine. Other optional ingredients may also bepresent.

Substances for use herein as co-ingredients or flavoring adjuvants arewell known in the art for such use, being extensively described in therelevant literature. It is a requirement that any such material be"ingestibly" acceptable and thus non-toxic and otherwise non-deleteriousparticularly from an organoleptic standpoint whereby the ultimate flavorand/or aroma of the consumable material used is not caused to haveunacceptable aroma and taste nuances. Such materials may, in general, becharacterized as flavoring adjuvants or vehicles comprising broadlystabilizers, thickeners, surface active agents, conditioners, otherflavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxy-anisole (mixture of 2- and3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials, lipids,carbohydrates; starches, pectins and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose, corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike, starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like,colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcoum chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, gerrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, cortonal, diacetyl, 2-methyl butanal,β,β-dimethyl acrolein, methyl-n-amyl ketone, n-hexanal, 2-hexenal,isopentanal, hydrocinnanic aldehyde, cis-3-hexenal, 2-heptenal nonylaldehyde, 4-(p-hydroxy-phenyl)-2-butanone, alpha-ionone, beta-ionone,methyl-3-butanone, benzaldehyde, β-damascone, β-damascenone,acetophenone, 2-heptanone, o-hydroxyacetophenone,2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal,2-phenyl-2-hexenal, 2-phenyl-2-pentenal, furfural, 5-methyl furfural,cinnamaldehyde, beta-cyclohomocitral, 2-pentanone, 2-pentenal andpropanal; alcohols such as 1-butanol, benzyl alcohol, 1-borneol,trans-2-buten-1-ol, ethanol, geraniol, 1-hexanol, 2-heptanol,trans-2-hexenol-1, cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol,1 -penten-3-ol, p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchylalcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate,eugenol, linalool, 2-heptanol, acetoin; esters, such as butyl acetate,ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, n-hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethyl naphthalene, dodecane, methyl diphenyl, methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane, tetramethylnaphthalene, tridecane, trimethyl naphthalene, undecane, caryophyllene,1-phellandrene, p-cymene, 1-alpha-pinene; pyrazines, such as2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils,such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute,orris absolute, lemon essential oil, Bulgarian rose, yara yara andvanilla; lactones, such as δ-nonalactone; sulfides, e.g., methyl sulfideand other materials such as maltol, acetoin and acetals (e.g.,1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the tertiary pentamethylindanolderivative(s) of our invention by not covering or spoiling theorganoleptic properties (aroma and/or taste) thereof; (ii) benon-reactive with one or more of the tertiary pentamethylindanolderivatives of our invention and (iii) be capable of providing anenvironment in which the tertiary pentamethylindanol derivative(s) ofour invention can be dispersed or admixed to provide a homogeneousmedium. In addition, selection of one or more flavoring adjuvants, aswell as the quantities thereof will depend upon the precise organolepticcharacter desired in the finished product. Thus, in the case offlavoring compositions, ingredient selection will vary in accordancewith the foodstuff, chewing gum, medicinal product or toothpaste orchewing tobacco to which the flavor and/or aroma are to be imparted,modified, altered or enhanced. In contradistinction, in the preparationof solid products, e.g., simulated foodstuffs, ingredients capable ofproviding normally solid compositions should be selected such as variouscellulose derivatives.

As will be appreciated by those skilled in the art, the amount oftertiary pentamethylindanol derivatives thereof of our inventionemployed in a particular instance can vary over a relatively wide range,depending upon the desired organoleptic effects to be achieved. Thus,correspondingly greater amounts would be necessary in those instanceswherein the ultimate food composition to be flavored (e.g., a"raisin-rum cake") is relatively bland to the taste, whereas relativelyminor quantities may suffice for purposes of enhancing the compositionmerely deficient in natural flavor or aroma, (e.g., when actual raisinsand rum are present in the foodstuff such as the cake). The primaryrequirement is that the amount selected by effective, i.e., sufficientto alter, modify or enhance the organoleptic characteristics of theparent composition, whether foodstuff per se, chewing gum per se,medicinal product per se, toothpaste per se, chewing tobacco per se orflavoring composition.

The use of insufficient quantities of one or more tertiarypentamethylindanol derivatives of our invention will, of course,substantially vitiate any possibility of obtaining the desired resultswhile excess quantities prove needlessly costly and in extreme cases,may disrupt the flavoraroma balance, thus proving self-defeating.Accordingly, the terminology "effective amount" and "sufficient amount"is to be accorded a significance in the content of the present inventionconsistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions, chewing tobaccocompositions and toothpaste compositions, it is found that quantities ofone or more tertiary pentamethylindanol derivatives of our inventionranging from a small but effective amount, e.g., about 0.05 parts permillion up to about 150 parts per million based on total foodcomposition or chewing gum composition, or medicinal product compositionor tobacco composition or chewing tobacco composition are suitable.Concentrations in excess of the maximum quantity stated are not normallyrecommended since they fail to provide commensurate enhancement oforganoleptic properties. In those instances where one or more tertiarypentamethylindanol derivatives of our invention are added to thefoodstuff as an integral component of a flavoring composition, it is, ofcourse, essential that the total quantity of flavoring compositionemployed be sufficient to yield an effective concentration of one ormore tertiary pentamethylindanol derivatives of our invention in thefoodstuff product.

Food flavoring compositions containing one or more of the compoundsprepared in accordance with the present invention preferably contain oneor more tertiary pentamethylindanol derivatives in concentrationsranging from about 0.02% up to about 15% by weight of the total weightof said flavoring composition.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing one or more of the tertiarypentamethylindanol derivatives of our invention prepared in accordancewith our invention with, for example, gum arabic, gum tragacanth,xanthan gum, carrageenan and the like, and thereafter spray-drying theresultant mixture whereby to obtain the particulate solid product.Pre-prepared flavor mixes in powder form, e.g., a fruit flavored or rumflavored powder mix are obtained by mixing the dried solid components,e.g., starch, sugar and the like and one or more tertiarypentamethylindanol derivatives of our invention in a dry blender untilthe requisite degree of uniformity is achieved.

It is presently preferred to combine one or more tertiarypentamethylindanol derivatives of our invention with at least one of thefollowiing adjuvants:

p-Hydroxybenzyl acetone;

Genaniol;

Cassia Oil;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Eugenol;

Vanillin;

Caryophyllene;

Methyl cinnamate;

Guiacol;

Ethyl pelargonate;

Cinnamaldehyde;

Methyl Anthranilate;

5-Methyl furfural;

Isoamyl Acetate;

Isobutyl acetate;

Cuminaldehyde;

Alpha ionone;

Cinnamyl formate;

Ethyl butyrate;

Methyl cinnamate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Furfural;

Ethyl acetate;

Anethol;

2,3-Dimethyl pyrazine;

2-Ethyl-3-methyl pyrazine;

3-Phenyl-4-pentenal;

2-Phenyl-2-hexenal;

2-Phenyl-2-pentenal;

3-Phenyl-4-pentenal diethyl acetal;

β-Damascone (1-crotonyl-2,6,6-trimethylcyclohex-1-ene);

β-Damascenone (1-crotonyl-2,6,6-trimethylcyclohexa-1,3-diene);

Beta-cyclohomocitral (2,6,6-trimethylcyclohex-1-ene carboxaldehyde);

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine (4-allyl-1,2,6-trimethoxybenzene);

Isoelemecine (4-propenyl-1,2,6-trimethoxybenzene);

2-(4-Hydroxy-4-methylpentyl) norbornadiene rum essence

3-hydroxy butyric acid;

2-hydroxy butyric acid;

N-methyl anthranilate cyclotene;

ethyl cyclotene;

n-propyl cyclotene; and

gin berry essence.

One of the tertiary pentamethylindanol derivatives prepared inaccordance with the process of our invention and one or more auxiliaryperfume ingredients including, for example, alcohols other than thetertiary pentamethylindanol derivatives of our invention, aldehydes,ketones, terpenic hydrocarbons, nitriles, esters, lactones, naturalessential oils and synthetic essential oils may be admixed so that thecombined odors of the individual components produce a pleasant anddesired fragrance, particularly, and preferably, in piney fragrances andpatchouli fragrances. Such perfume compositions usually contain (a) themain note or the "bouquet" or foundation stone of the composition; (b)modifieres which round off and accomapny the main note; (c) fixativeswhich include odorous substances which lend a particular note to theperfume throughout all states of evaporation and substances which retardevaporation; and (d) topnotes which are usually low-boilingfresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however, theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one of thetertiary pentamethylindanol derivatives prepared in accordance with theprocesses of our invention can be used to alter, modify, or enhance thearoma characteristics of a perfume composition, for example, byutilizing or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of one of the tertiary pentamethylindanol derivativesprepared in accordance with the processes of our invention which will beeffective in perfume compositions as well as in perfumed articles (e.g.,anionic, nonionic, cationic, or zwitterionic detergents, soaps andfabric softener compositions and articles) and colognes depends uponmany factors including the other ingredients, their amounts of theeffects which are desired. It has been found that perfume compositionscontaining as little as 0.01% of one of the tertiary pentamethylindanolderivatives prepared in accordance with the processes of our inventionand less 50% of one of the tertiary pentamethylindanol derivativesprepared in accordance with the processes of our invention or even less(e.g., 0.005%) can be used to impart a leafy, patchouli-like,vertiver-like, ginseng-like, piney, rooty, woody, camphoraceous aromawith leafy, green, camphoraceous, woody, patchouli-like, musk, rooty,earthy and piney undertones to soaps, cosmetics, anionic, cationic,nonionic, or zwitterionic detergents, fabric softener compositions,fabric softener articles, perfumed polymers or other amounts. The amountemployed can range up to 70% of the fragrance components and will dependon considerations of cost, nature of the end product, the effect desiredon the finished product and the particular fragrance sought.

One or more of the tertiary pentamethylindanol derivatives prepared inaccordance with the processes of our invention are useful (taken alongor together with other ingredients in perfume compositions) as (an)olfactory component(s) in detergents and soaps, space odorants anddeodorants, perfumes, colognes, toilet water, bath preparations, such ascreams, deodorants, hand lotions and sun screens; powders, such astalcs, dusting powders, face powders, perfumed polymers and the like.When used as (an) olfactory component(s) as little as 0.2% of one orboth of the tertiary pentamethylindanol derivatives of our invention,prepared in accordance with the process of our invention, will sufficeto impart an intense leafy, patchouli-like, vetiver-like, ginseng-like,piney, rooty, woody, camphoraceous aroma with leafy, green,camphoraceous, woody, patchouli-like, musk, rooty, earthy and pineyundertones to patchouli formulations and to vertiver formulations and topine formulations. Generally, no more than 6% of one or both of thetertiary pentamethylindanol derivatives of our invention produced inaccordance with the processes of our invention based on the ultimate endproduct are required in the perfumed article composition. Accordingly,the range of one or more of the tertiary pentamethylindanol derivativesof our invention in a perfumed article may vary from about 0.2% up toabout 6% by weight of the ultimate perfumed article.

In addition, the perfume compositions or fragrance compositions of ourinvention can contain a vehicle or carrier for one or both of thetertiary pentamethylindanol derivatives prepared in accordance with theprocesses of our invention. The vehicle can be a liquid, such as anon-toxic alcohol, e.g., ethyl alcohol, a glycol, e.g., propylene glycolor the like. The carrier can also be an absorbent solid, such as a gum(e.g., gum arabic, xanthan or guar gum) or components for encapsulatingthe composition (such as gelatin as by coacervation or such as aurea-formaldehyde pre-polymer when forming a urea-formaldehyde polymerwall around a liquid perfume center).

It will thus be apparent that one or both of the tertiarypentamethylindanol derivatives of our invention produced in accordancewith the processes of our invention can be utilized to alter, modify orenhance sensory properties, particularly organoleptic properties such asflavors and/or fragrances of a wide variety of consumable materials.

Furthermore, one or both of the tertiary pentamethylindanol derivativesof our invention prepared in accordance with the processes of ourinvention are capable of supplying and/or potentiating certain flavorand aroma notes usually lacking in many smoking tobacco flavors andsubstitute tobacco flavors provided herein.

As used herein in regard to smoking tobacco flavors, the terms "alter"and "modify" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland smoking tobacco, smoking tobaccosubstitutes, or smoking tobacco flavor formulations or augmenting theexisting flavor characteristic where a natural flavor is deficient insome regard or supplementing the existing flavor impression to modifyits quality, character or taste".

As used herein, the term "enhance" is intended to mean theintensification (without change in kind of quality of aroma or taste) ofone or more taste and/or aroma nuances present in the organolepticimpression of smoking tobacco or a smoking tobacco substitute or asmoking tobacco flavor.

Our invention thus provides an organoleptically improved smoking tobaccoproduct and additives therefor, as well as methods of making the samewhich overcome specific problems heretofore encountered in whichspecific desired oriental, and Turkish tobacco-like notes on smoking andprior to smoking in the main stream and in the side stream are createdor enhanced and may be readily controlled and maintained at the desireduniform level regardless of variations in the tobacco components of theblend.

Our invention further provides improved smoking tobacco additives andmethods whereby various oriental and Turkish tobacco notes prior tosmoking and on smoking are imparted (in the main stream and in the sidestream) to smoking tobacco products and may be readily varied andcontrolled to produce the desired uniform flavor characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient at leastone of the two tertiary pentamethylindanol derivatives of our inventionprepared in accordance with the processes of our invention.

In addition to the one or both tertiary pentamethylindanol derivativesof our invention prepared in accordance with the processes of ourinvention, other flavoring and aroma additives may be added to thesmoking tobacco materials or substitute therefor either separately or inadmixture with one or both of the tertiary pentamethylindanolderivatives of our invention as follows:

(i) Synthetic Materials

Beta-ethyl-cinnamaldehyde;

Beta-cyclohomocitral;

Eugenol;

Dipentene;

β-Damascenone;

β-Damascone;

Maltol;

Ethyl maltol;

Delta-undecalactone;

Delta-decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1,b]-furan;

4-Hydroxy hexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

(ii) Natural Oils

Celery seed oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg oil; and

Origanum oil.

An aroma and flavoring concentrate containing one or both of thetertiary pentamethylindanol derivatives of our invention and, ifdesired, one or more of the above-identified additional flavoringadditives may be added to the smoking tobacco material, to the filter orto the leaf or paper wrapper. The smoking tobacco material may beshredded, cured, cased and blended tobacco material or reconstitutedtobacco material or tobacco substitutes (e.g., lettuce leaves) ormixtures thereof. The proportions of flavoring additives may be variedin accordance with the taste but insofar as the enhancement or theimparting of natural and/or oriental notes, we have found thatsatisfactory results are obtained if the proportion by weight of the sumtotal of one or both of the tertiary pentamethylindanol derivatives ofour invention to smoking tobacco material is between 250 ppm and 1,500ppm (0.025%-0.15%) of the active ingredients to the smoking tobaccomaterial. We have further found that satisfactory results are obtainedif the proportion by weight of the sum total of one or both of thetertiary pentamethylindanol derivatives of our invention is between2,500 and 15,000 ppm (0.25%-1.50%).

Any convenient method for incorporating one or both of the tertiarypentamethylindanol derivatives prepared in accordance with the processof our invention in the tobacco product may be employed. Thus, one orboth of the tertiary pentamethylindanol derivatives of our inventiontaken alone or along with other flavoring additives may be dissolved ina suitable solvent such as ethanol, pentane, diethyl ether and/or otherorganic solvents and the resulting solution may be either sprayed on thecured, cased and blended tobacco material or the tobacco material may bedipped into such solution. Under certain circumstances a solutioncontaining one or both of the tertiary pentamethylindanol derivatives ofour invention prepared in accordance with the process of our inventiontaken alone or taken further together with other flavoring additives asset forth above mey be applied by means of a suitable applicator such asa brush or roller on the paper or leaf wrapper for the smoking product,it may be applied to the filter by either spraying, or dipping, orcoating.

Furthermore, it will be apparent that only a portion of the smokingtobacco or substitute therefor need be treated and the thus treatedtobacco may be blended with other tobaccos before the ultimate tobaccoproduct is formed. In such cases, the tobacco treated may have one orboth of the tertiary pentamethylindanol derivatives of our invention inexcess of the amount or concentrations above indicated so that whenblended with other tobaccos, the final product will have the percentagewithin the indicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic Burley tobacco is sprayed with a 20% ethyl alcoholsolution of a 50:50 mixture of the compounds having the structures:##STR41## in an amount to provide a tobacco composition containing 800ppm by weight of the mixture of compounds having the structures:##STR42##

Thereafter, the alcohol is removed by evaporation and the tobacco ismanufactured into cigarettes by the usual techniques. The cigarette,when treated as indicated, has a desired and pleasing aromas prior tosmoking which can be described as oriental-like and Turkish and onsmoking in the main stream and the side stream a sweet oriental-like andTurkish tobacco-like aroma with faint but aesthetically pleasing fruityand rum-like undertones.

While our invention is particularly useful in the manufacture of smokingtobacco such as cigarette tobacco, cigar tobacco and pipe tobacco, othersmoking tobacco products formed from sheeted tobacco dust or fines mayalso be used. Likewise one or both of the tertiary pentamethylindanolderivatives of our invention can be incorporated with materials such asfilter tip materials, seam paste, packaging materials and the like whichare used along with tobacco to form a product adapted for smoking.Furthermore, one or both of the tertiary pentamethylindanol derivativesof our invention can be added to certain tobacco substitutes of naturalor synthetic origin (e.g., dried lettuce leaves) and, accordingly, bythe term "tobacco" is used throughout this specification is meant anycomposition intended for human consumption by smoking or otherwise,whether composed of tobacco plant parts or substitute materials or both.

The following Examples I, II, III and V illustrate methods of ourinvention used to manufacture the tertiary pentamethylindanolderivatives of our invention. Example IV sets forth a technique of theprior art. Examples following Example V serve to illustrate theirorganoleptic utilities of the tertiary pentamethylindanol derivatives ofour invention.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF5,6-DIHYDRO-1,1,2,3,3-PENTAMETHYL-3A(4H)-INDANOL

Reaction: ##STR43##

Into a 1-liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle is placed the following materials:

    ______________________________________                                        Tetrahydro pentamethylindane                                                                          160 grams                                             epoxide having the structure:                                                  ##STR44##                                                                    Aluminum isopropoxide   160 grams                                             Anhydrous toluene       400 ml                                                ______________________________________                                    

The resulting reaction mass is heated to reflux and refluxed for aperiod of twenty four hours. At the end of the twenty four hour period,600 ml water and 100 ml 50% sodium hydroxide is added to the reactionmass whereby the reaction mass now has a pH of between 10 and 12.

The reaction mass is poured into a separatory funnel and the organiclayer is separated from the aqueous layer. The organic phase is washedtwice with an equal volume of water and twice with an equal volume ofsaturated sodium chloride solution.

The crude material weighing 472.8 grams is dried and rushed over througha 2" splash column yielding the following fractions:

    ______________________________________                                                  Vapor        Liquid  Vacuum                                         Fraction  Temp.        Temp.   mm/Hg.                                         No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         66/75        82/88   1.0                                            2         82           93      1.0                                            3         84           99      0.95                                           4         80           210     0.94                                           ______________________________________                                    

Fractions 2, 3 and 4 are bulked and redistilled on a 12" Goodloe columnyielding the following fractions:

    ______________________________________                                                  Vapor        Liquid  Vacuum                                         Fraction  Temp.        Temp.   mm/Hg.                                         No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         61           115     1.0                                            2         57           106     0.8                                            3         68           105     1.3                                            4         71           107     0.8                                            5         74           109     0.8                                            6         74           109     0.8                                            7         74           113     0.8                                            8         76           170     0.8                                            9         75           250     0.8                                            ______________________________________                                    

FIG. 1 is the GLC profile for the crude reaction product prior todistillation.

FIG. 2 is the GLC profile for Fraction 2 of the first distillation.

FIG. 3 is the GLC profile for Fraction 7 of the second distillation.

FIG. 4 is the GC-MS profile for the compound having the structure:##STR45## produced according to this example.

FIG. 5 is the NMR spectrum for Fraction 7 of the foregoing distillationwhich is for the compound having the structure: ##STR46## (conditions:Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 6 is the infra-red spectrum for the compound having the structure:##STR47## produced according to this example.

The resulting product having the structure: ##STR48## from a fragrancestandpoint has a leafy, patchouli-like, vetiver-like and ginseng-likearoma with leafy, green, camphoraceous, woody, patchouli-like and muskundertones. From a flavor standpoint the compound having the structure:##STR49## has a musky, patchouli-like and earthy aroma with a muskytaste at 1.0 ppm causing it to be useful in walnut and blackberryflavored foodstuffs.

From a tobacco flavor point of view the compound having the structure:##STR50## has a woody, oriental aroma and taste profile prior to and onsmoking in the main stream and the side stream and gives rise to Turkishtobacco-like nuances in the main stream and the side stream on smoking.

EXAMPLE II PREPARATION OFTETRAHYDRO-1,1,2,3,3-PENTAMETHYL-3A(4H)-INDANOL

Reaction: ##STR51##

Into a 500 ml reaction flask equipped with reflux condenser,thermometer, heating mantle and stirrer is placed 250 ml of ethylenediamine. To the ethylene diamine, 52.0 grams (0.25 moles) of tetrahydropentamethylindane epoxide having the structure: ##STR52## is added overa period of 10 minutes.

5.25 Grams of lithium wire is added to the reaction mass over a periodof 10 minutes and the resulting mixture is heated, with stirring to 50°C. The reaction mass exotherms to 75°-80° C. and is cooled rapidly downto 50° C. The reaction mass is maintained, with stirring at 50° C. for aperiod of 1.5 hours. GLC sampling indicates completion of the reaction.

The reaction mass is quenched with 200 ml of water and extracted with200 ml diethyl ether. The ether extract is dried over anhydrous sodiumsulfate and stripped of solvent and then distilled to yield 40 grams ofproduct, a compound defined according to the structure: ##STR53##

The distillation is carried out using a micro vigreux column yieldingthe following fractions:

    ______________________________________                                                 Vapor   Liquid    Vacuum Weight                                      Fraction Temp.   Temp.     mm/Hg. of Fraction                                 No.      (°C.)                                                                          (°C.)                                                                            Pressure                                                                             (gms.)                                      ______________________________________                                        1        50/65   86/92     1.8     0.8                                        2        87       96       1.8     1.0                                        3        90      103       1.8    14.0                                        4        90      120       1.8    16.0                                        5        90      180       1.8    16.0                                        ______________________________________                                    

FIG. 7 is the GLC profile for Fraction 5 of the foregoing distillation.(Conditions: Carbowax column programmed at 100°-220° C. at 8° C. perminute).

FIG. 8 is the NMR spectrum for Fraction 5 of the foregoing distillationwhich is for the compound having the structure: ##STR54## (conditions:Field strength: 100 MHz; Solvent; CFCl₃).

From a fragrance standpoint the resulting product has a patchouli-like,piney, rooty, woody and camphoraceous aroma profile with rooty, earthy,camphoraceous, woody and piney undertones. From a flavor standpoint thesubject compound has a patchouli-like aroma and taste profile at 10 ppmcausing it to be useful in walnut flavor foodstuffs.

From a tobacco flavor standpoint the resulting compound having thestructure: ##STR55## has a woody, oriental and Turkish tobacco-likearoma and taste profile both prior to and on smoking in the main streamand in the side stream.

EXAMPLE III PREPARATION OF5,6-DIHYDRO-1,1,2,3,3-PENTAMETHYL-3A(4H)-INDANOL

Reaction: ##STR56##

Into a 250 ml reaction flask equipped with stirrer, thermometer, refluxcondenser and heating mantle are placed the following materials:

(i) 50.0 grams (0.24 moles) of tetrahydro pentamethylindane epoxidedefined according to the structure: ##STR57## (ii) 29.56 grams (0.12moles) of aluminum trisecondary butoxide defined according to thestructure: ##STR58## wherein R is secondary butyl; and (iii) 50 mltoluene.

The reaction mass is refluxed for a period of five hours during whichtime the reaction is followed by GLC. At the end of the five hourperiod, 100 ml of water is added to the reaction mass and the resultingmixture is then admixed with 50 ml of 50% aqueous sodium hydroxidewhereby the resulting mixture has a pH of between 10 and 12.

The organic phase is separated from the aqueous phase and the organicphase is washed with one 100 ml portion of water, stripped of solventand distilled yielding the following fractions:

    ______________________________________                                                  Vapor        Liquid  Vacuum                                         Fraction  Temp.        Temp.   mm/Hg.                                         No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         65/70        80/82   3.5/3.0                                        2         70            90     3.0                                            3         80            95     3.0                                            4         91           117     2.3                                            5         90           160     2.3                                            ______________________________________                                    

FIG. 9 is the GLC profile for Fraction 3 of the foregoing distillationcontaining the compound having the structure: ##STR59##

The resulting compound having the structure: ##STR60## from a fragrancestandpoint has a leafy, patchouli-like, vetiver-like and ginseng-likearoma profile with leafy, green, camphoraceous, woody, patchouli-likeand musk undertones. From a flavor standpoint it has a musky,patchouli-like and earthy aroma with a musky taste at 1.0 ppm causing itto be useful in walnut and blackberry flavored foodstuffs. From atobacco flavor point of view, the compound has a woody and orientalaroma and taste profile both prior to and on smoking in the main streamand the side stream.

EXAMPLE IV PRIOR ART PREPARATION OF4,5,6,7-TETRAHYDRO-1,1,2,3,3-PENTAMETHYL-4-INDANOL

Reaction: ##STR61##

Into a 2-liter reaction vessel are placed 831 ml of toluene and 226.9grams (1.11 moles) of aluminum isopropoxide. The mixture is heated toreflux and while refluxing, over a one hour period, tetrahydropentamethylindane epoxide having the structure: ##STR62## is added tothe reaction mass. The reaction mass is continued to be refluxed for aperiod of twelve hours while being monitored by GLC analysis. Anadditional 0.5 moles of aluminum isopropoxide is added (101.5 grams) atthe end of the twelve hour period and the refluxing is continued for anadditional eight hours. At the end of the twenty hour period, anadditional 50.7 grams of aluminum triisopropylate is added and thereaction mass is continued to be refluxed for an additional twenty twohours (total reflux time 42 hours).

The reaction mass is then washed with one 300 ml portion of aqueous 20%sulfuric acid followed by one 300 ml portion of water and then followedby one 300 ml portion of aqueous sodium bicarbonate (saturated). Theorganic layer is stripped of solvent and then distilled on a 12"stonepacked column yielding the following fractions:

    ______________________________________                                                  Vapor        Liquid  Vacuum                                         Fraction  Temp.        Temp.   mm/Hg.                                         No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         45/74        109/101 8.5/7.0                                        2         68           107     7.0                                            3         79           111     7.0                                            4         90           115     7.0                                            5         90           125     7.0                                            6         47           235     7.0                                            ______________________________________                                    

Fractions 2-6 of this distillation product are bulked and redistilled ona spinning band column yielding the following fractions:

    ______________________________________                                                  Vapor        Liquid  Vacuum                                         Fraction  Temp.        Temp.   mm/Hg.                                         No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         40/45        90/95   2.4/2.0                                        2         65           105     2.0                                            3         60           106     2.0                                            4         60           109     2.0                                            5         60           110     2.0                                            6         68           120     2.0                                            7         68           143     2.0                                            8         30           210     2.0                                            ______________________________________                                    

FIG. 10 is the GLC profile for Fraction 4 of the first distillationcontaining the compound having the structure: ##STR63##

FIG. 11 is the GLC profile for Fraction 4 of the second distillation;the redistillation of bulked Fractions 2-6 of the first distillationcontaining the compound having the structure: ##STR64## (conditions:Carbowax column programmed at 100°-220° C. at 8° C. per minute).

FIG. 12 is the NMR spectrum for Fraction 4 of the second distillationcontaining the compound having the structure: ##STR65## (conditions:Field strength: 100 MHz; Solvent: CFCl₃).

The resulting product also contains the compound having the structure:##STR66## in an amount of approximately 50% by weight.

The resulting mixture containing the compound having the structure:##STR67## has a woody, balsamic aroma approximately one-third theintensity of the compound produced according to Examples I and IIIhaving the structure: ##STR68## in the absence of the compound havingthe structure: ##STR69##

EXAMPLE V PREPARATION OF TETRAHYDRO-1,1,2,3,3-PENTAMETHYL-3A(4H)-INDANOL

Reaction: ##STR70##

Into a 250 ml reaction vessel equipped with stirrer, thermometer andreflux condenser is placed a mixture of 11 grams (0.3 moles) of lithiumaluminum hydride and 100 ml of diglyme. The resulting mixture is cooledwith stirring to 0° C. Over a period of 30 minutes, 62.4 grams (0.3moles) of tetrahydro pentamethylindane epoxide having the structure:##STR71## is slowly added to the resulting mixture.

The resulting mixture is heated to 174° C. (reflux temperature) andrefluxed at 174° C. for a period of ten hours. GLC monitoring indicatescompletion of the reaction.

At the end of the ten hour period while maintaining the reaction mass at0° C., the reaction mass is quenched with the following:

(i) 11 ml water;

(ii) 11 ml 15% sodium hydroxide; and

(iii) 33 ml water.

The organic phase is separated from the aqueous phase and the organicphase is filtered and distilled at 1 mm/Hg pressure (68% yield). Thisproduct has the structure: ##STR72##

EXAMPLE VI

The following Chypre formulation is prepared:

    ______________________________________                                        Ingredients       Parts by Weight                                             ______________________________________                                        Musk ambrette     40                                                          Musk ketone       60                                                          Coumarin          30                                                          Oil of bergamot   150                                                         Oil of lemon      100                                                         Methyl ionone     50                                                          Hexyl cinnamic aldehyde                                                                         100                                                         Hydroxycitronella 100                                                         Oil of lavender   50                                                          Texas cedarwood oil                                                                             85                                                          Virginia cedarwood oil                                                                          30                                                          Oil of sandalwood 40                                                          (East Indies)                                                                 Isoeugenol        20                                                          Eugenol           10                                                          Benzyl acetate    30                                                          β-phenyl ethyl alcohol                                                                     40                                                          α-phenyl ethyl alcohol                                                                    30                                                          Oakmoss absolute  30                                                          Vetiver oil Venezuela                                                                           25                                                          Compound having the                                                                             25                                                          structure:                                                                     ##STR73##                                                                    prepared according                                                            to Example I or                                                               Example III                                                                   ______________________________________                                    

The compound having the structure: ##STR74## prepared according toExample I or III imparts to this Chypre formulation an intensepatchouli-like, vetiver-like, leafy, ginseng aroma with leafy, green,camphoraceous, woody, patchouli and musk undertones. Accordingly, thisformulation can be described as Chypre having leafy, patchouli-like,vetiver-like and ginseng nuances with leafy, green, camphoraceous,woody, patchouli and musk undertones.

EXAMPLE VII PINE FRAGRANCE

The following pine fragrance formulation is produced:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Isobornyl acetate   100                                                       Camphor             10                                                        Terpeineol          25                                                        Fir balsam absolute 20                                                        (50% in diethyl phthalate)                                                    Coumarin             4                                                        Linalool            30                                                        Fenchyl alcohol     10                                                        Anethol             12                                                        Lemon terpenes washed                                                                             50                                                        Borneol              5                                                        Galbanum oil         5                                                        Turpentine Russian  150                                                       Eucalyptol          50                                                        2,2,6-trimethyl-1-cyclohexene-                                                                    12                                                        1-carboxaldehyde                                                              Maltol (1% in diethyl phthalate)                                                                   5                                                        The compound having 28                                                        the structure:                                                                 ##STR75##                                                                    produced according                                                            to Example II or V.                                                           ______________________________________                                    

The compound having the structure: ##STR76## prepared according toExamples II or V imparts to this pine fragrance an excellentpatchouli-like, rooty, woody, camphoraceous, aroma nuance with rooty,earthy, camphoraceous and woody undertones. Accordingly, thisformulation can be described as piney with rooty, patchouli-like, woody,camphoraceous nuances and rooty, earthy, camphoraceous and woodyundertones.

EXAMPLE VIII PREPARATION OF COSMETIC POWDER COMPOSITIONS

Cosmetic powder compositions are prepared by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table II below. Each of the cosmetic powder compositions has anexcellent aroma as described in Table II below:

                  TABLE II                                                        ______________________________________                                        Substance     Aroma Description                                               ______________________________________                                         ##STR77##    A leafy, patchouli-like, vetiver-like and ginseng-like                        aroma with leafy, green, camphoraceous, woody, patchouli-lik                  e and musk undertones.                                           ##STR78##    A patchouli-like, piney, rooty, woody, camphoraceous aroma                    with rooty, earthy, camphoraceous, woody, and piney                           undertones.                                                     Pefume composition                                                                          A leafy, pathcouli-like, vetiver-                               of Example VI like and ginseng nuances                                                      with leafy, green, camphoraceous,                                             woody, patchouli and musk undertones                            Perfume composition                                                                         A piney aroma with rooty, patchouli-                            of Example VII                                                                              like, woody, camphoraceous nuances                                            and rooty, earthy, camphoraceous                                              and woody undertones.                                           ______________________________________                                    

EXAMPLE IX PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents (Lysine sale of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976) with aroma nuances as set forth in Table II of ExampleVIII are prepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30% and 0.35%of the substance set forth in Table II of Example VIII. They areprepared by adding and homogeneously mixing the appropriate quantity ofsubstance set forth in Table II of Example VIII below in the liquiddetergent. The detergents all possess excellent aromas as set forth inTable II of Example VIII, the intensity increasing with greaterconcentrations of substance as set forth in Table II of Example VIII.

EXAMPLE X PREPARATION OF COLOGNES AND HANDKERCHIEF PERFUMES

Compositions as set forth in Table II of Example VIII are incorporatedinto colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%and 5.0% in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions;and into handkerchief perfumes at concentrations of 15%, 20%, 25% and30% (in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions).Distinctive and definitive fragrances as set forth in Table II ofExample VIII are imparted to the colognes and to the handkerchiefperfumes at all levels indicated.

EXAMPLE XI PREPARATION OF SOAP COMPOSITIONS

One hundred grams of soap chips [per sample] (IVORY®, produced by theProcter & Gamble Company of Cincinnati, Ohio), are each mixed with onegram samples of substances as set forth in Table II of Example VIIIuntil homogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 8 atmospheres pressure at 180°C. for a period of three hours and the resulting liquids are placed intosoap molds. The resulting soap cakes, on cooling, manifest aromas as setforth in Table II of Example VIII.

EXAMPLE XII PREPARATION OF SOLID DETERGENT COMPOSITIONS

Detergents are prepared using the following ingredients according toExample I of Canadian Pat. No. 1,007,948:

    ______________________________________                                        Ingredient         Percent By Weight                                          ______________________________________                                        "Neodol ® 45-11 (a C.sub.14 -C.sub.15                                                        12                                                         alcohol ethoxylated with                                                      11 moles of ethylene oxide                                                    Sodium carbonate   55                                                         Sodium citrate     20                                                         Sodium sulfate, water                                                                            q.s.                                                       brighteners                                                                   ______________________________________                                    

This detergent is a phosphate-free detergent. Samples of 100 grams eachof this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams ofeach of the substances as set forth in Table II of Example VIII. Each ofthe detergent samples has an excellent aroma as indicated in Table II ofExample VIII.

EXAMPLE XIII Utilizing the procedure of Example I at column 15 of U.S.Pat. No. 3,632,396, nonwoven cloth substrates useful as dry-added fabricsoftening articles of manufacture are prepared wherein the substrate,the substrate coating and the outer coating and the perfuming materialare as follows:

1. A water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. An outer coating having the following formulation (m.p. about 150°F.):

57%--C₂₀₋₂₂ HAPS

22%--isopropyl alcohol

20%--antistatic agent

1%--of one of the substances as set forth in Table II of Example VIII.

Fabric softening compositions prepared according to Example I at column15 of U.S. Pat. No. 3,632,396 having aroma characteristics as set forthin Table II of Example VIII, consist of a substrate coating having aweight of about 3 grams per 100 square inches of substrate; a firstcoating on the substrate coating consisting of about 1.85 grams per 100square inches of substrate; and an outer coating coated on the firstcoating consisting of about 1.4 grams per 100 square inches ofsubstrate. One of the substances of Table II of Example VIII is admixedin each case with the outer coating mixture, thereby providing a totalaromatized outer coating weight ratio to substrate of about 0.5:1 byweight of the substrate. The aroma characteristics are imparted in apleasant manner to the head space in a dryer on operation thereof ineach case using said dryer-added fabric softener non-woven fabrics andthese aroma characteristics are described in Table II of Example VIII.

EXAMPLE XIV HAIR SPRAY FORMULATIONS

The following hair spray formulation is prepared by first dissolvingPVP/VA E-735 copolymer manufactured by the GAF Corporation of 140 West51st Street, New York, N.Y., in 91.62 grams of 95% food grade ethanol,8.0 grams of the polymer is dissolvedd in the alcohol. The followingingredients are added to the PVP/VA alcoholic solution:

    ______________________________________                                        Ingredients          Weight Percent                                           ______________________________________                                        Dioctyl sebacate     0.05                                                     Benzyl alcohol       0.10                                                     Dow Corning 473 fluid                                                                              0.10                                                     (prepared by the Dow Corning                                                  Corporation)                                                                  Tween 20 surfactant  0.03                                                     (prepared by ICI America                                                      Corporation)                                                                  One of the perfumery substances                                                                    0.10                                                     as set forth in Table II of                                                   Example VIII                                                                  ______________________________________                                    

The perfuming substances as set forth in Table II of Example VIII addaroma characteristics as set forth in Table II of Example VIII which arerather intense and aesthetically pleasing to the users of the soft-feel,goodhold pump hair sprays.

EXAMPLE XV CONDITIONING SHAMPOOS

Monamid CMA (prepared by the Mona Industries Company) (3.0 weightpercent) is melted with 2.0 weight percent coconut fatty acid (preparedby Procter & Gamble Company of Cincinnati, Ohio); 1.0 percent ethyleneglycol distearate (prepared by the Armak Corporation) andtriethanolamine (a product of Union Carbide Corporation) (1.4 weightpercent). The resulting melt is admixed with Stepanol WAT produced bythe Stepan Chemical Company (35.0 weight percent). The resulting mixtureis heated to 60° C. and mixed until a clear solution is obtained (at 60°C.).

Gafquat®755N polymer (manufactured by GAF Corporation of 140 West 51stStreet, New York, N.Y.) (5.0 weight percent) is admixed with 0.1 weightpercent sodium sulfite and 1.4 weight percent polyethylene glycol 6000distearate produced by Armak Corporation.

The resulting material is then mixed and cooled to 45° C. and 0.3 weightpercent of perfuming substance as set forth in Table II of Example VIIIis added to the mixture. The resulting mixture is cooled to 40° C. andblending is carried out for an additional one hour in each case. At theend of this blending period, the resulting material has a pleasantfragrance as indicated in Table II of Example VIII.

EXAMPLE XV TOBACCO FORMULATIONS

Tobacco mixtures are prepared by admixing the following ingredients:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Bright          40.1                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue-cured)                                                                             14.2                                                          Glycerine       2.8                                                           Water           5.3                                                           Cigarettes are prepared from this tobacco.                                    The following flavor formulation is prepared:                                 Ethyl butyrate  .05                                                           Ethyl valerate  .05                                                           Maltol          2.00                                                          Cocoa extract   26.00                                                         Coffee extract  10.00                                                         Ethyl alcohol   20.00                                                         Water           41.90                                                         ______________________________________                                    

The above stated tobacco flavor formulation is applied at the rate of1.0% to all of the cigarettes produced using the above tobaccoformulation. The cigarettes are divided into groups as follows:

Group A-treated with 500 ppm of the compound having the structure:##STR79## prepared according to either of Example I or Example III.

Group B-treated with 500 ppm of the compound having the structure:##STR80## prepared according to Example II or Example V.

Group C-not treated with any compounds (control cigarettes).

The control cigarettes and the experimental cigarettes of Groups A andB, which contain the compound defined according to the structures:##STR81## prepared according to Examples I, II, III and V, inclusive areevaluated by paired comparison and the results are as follows:

The experimental cigarettes of Groups A and B are found to have morebody in tobacco smoke flavor and a fuller body sensation. The tobacconotes are described as "Turkish-like" with oriental nuances both priorto and on smoking in the main stream and the side stream. The flavor ofthe tobacco on smoking is, in addition, sweeter and more aromatic. Allof the cigarettes are evaluated for smoke flavor with a 20 mm celluloseacetate flavor.

EXAMPLE XVII FLAVOR FORMULATIONS

At the rate of 0.4 ppm a 50:50 mixture of the compound having thestructure: ##STR82## and the compound having the structure: ##STR83## isadded to a slurry containing water and 70% by weight of chopped shelledwalnuts having an average particle diameter of 0.3 mm. The resultingslurry is then filtered and carefully dried at 45° F. in a forced airdryer. The resulting ground walnuts have a long-lasting, fresh walnutflavor even after remaining refrigerated in a standard refrigerator fora period of two weeks.

EXAMPLE XVIII BLACKBERRY JAM

At the rate of 0.15 ppm, the compound having the structure: ##STR84##prepared according to Example I or III is added to SMUCKERS® BlackberryPreserves. The resulting blackberry preserves retain their originalfresh flavor after being removed from the vacuum jar in which it wasoriginally marketed and the original blackberry flavor is retained for aperiod of six weeks when the resulting preserves are refrigerated in astandard kitchen refrigerator.

What is claimed is:
 1. A process for augmenting or enhancing the aromaor taste of a smoking tobacco composition comprising the step of addingto said smoking tobacco composition an aroma augmenting or enhancingquantity of a composition of matter selected from the group consistingof:(i) the compound having the structure: ##STR85## and (ii) thecompound having the structure: ##STR86##
 2. The process of claim 1wherein the smoking tobacco composition has added to it the compoundhaving the structure: ##STR87##
 3. The process of claim 1 wherein thesmoking tobacco composition has added to it the compound having thestructure: ##STR88##
 4. A process for augmenting or enhancing the aromaor taste of a smoking tobacco article comprising the step of adding tosaid smoking tobacco article an aroma augmenting or enhancing quantityof a composition of matter selected from the group consisting of:(i) thecompound having the structure: ##STR89## and (ii) the compound havingthe structure: ##STR90##
 5. The process of claim 4 wherein the smokingtobacco article has added to it the compound having the structure:##STR91##
 6. The process of claim 4 wherein the smoking tobacco articlehas added to it the compound having the structure: ##STR92##
 7. Asmoking tobacco article comprising a cylindrical body of smokingtobacco, longitudinally surrounded by a wrapper and having affixed toone end of said cylindrical body of tobacco, a tobacco filter whereincontained in said filter, said wrapper or said cylindrical body oftobacco in an aroma or taste augmenting enhancing amount is acomposition of matter selected from the group consisting of:(i) thecompound having the structure: ##STR93## and (ii) the compound havingthe structure: ##STR94##